Manufacture of azo dyes



-UNITED" T Patented May 19,1931 I f ast 5,714

PATENT oF FIoE RAINALD'BRIGHTMAN, or B AcxLnY, MANCfiESTERgENGLAND}Assrenon worm rnnrA CHEMICAL INDUSTRIES LIMITED, 01* wEsrMms'rnn'nNe ANnANUF CTURE or AZO was" No Drawing. Application 'filea'retruar iz, 1930,Serial 1104421959,. and in'Great Britain r rebruar ,21,1929.. I 131 1This invention relates to the manufacture. ofvalu'able new azo dyestuffswhich may be obtained by combining a diazotized' oxamic acid derivativeof a4:4-diaminodiphenylsulphide of the general formula oooHooiIO-s O-Ninwhere n represents 1 or 3 with one molecular proportion of any of theusual couplingcomponents. The coupling may be'performed in acid oralkaline solution as may be necessary.

The thus obtained dyestuffs may sented by the formula dyestufi's dyewool or regenerated celluloseor.

cellulose esters or ethersior instance acetate rayon in shades varyingfrom yellow'to vlolet to brown and are characterized by -yieldlng onreduction an oxamic acidderivative of a 4} 4diaminodiphenylsulphide ofthe gen al formula 1 p p a where n represents 1 or 3, and an amidatedcoupling component XNH where X representstheresidue of a couplingcomponent. Advanta'geous dyes areformed when the I diazotized oxamicacid derivative is coupled wherein n represents 1 or 3,

with an aminonaphthol sulphonic acid, the amino group of which may besubstituted. These dyes in the form of the free acid can be representedby the probable general formula on I time be repre' 2 and, I Irepresents 7 hydrogen or invention illustrated by thefollo'wingexarnples,in;which the parts 1 are by Weight.

Example '1.-216 parts of 4 a diamiiiodi-l phenyl sulphide,.m. p. 108?.6., are "boiled with 50 0 parts. of oxalic acid crystals and about 4000parts of water.

The 1diaminodiph y su phide goes: into solutionand'after some time awhite crystalline product separates. This is filtered hot, afterabout 20hours, washed iwith'warm water, and .thenstirred for a short time in alittle warm dilute hydrochloric acid to remove any unchanged base.' The4;aminodi-' Emample 2..280 parts'of 4 z fediaminodiphenylsulphide-U-oxamic acid is-finally fil I tered, washed and dried- It doesnot melt below 265 C.

phenyltrisulphide, m. p. 1229' 0., areboiled WithAOO parts of oxalicacid crystalsand about 4000'part'sof water for20vhoursw Theiz-aminodiphenyltrisulphide-'-oxamic acid isisolated and purifiedexactlyasdescribed in ipow- 7 Example 1.; It forms a pale yellowishderjwhieh does not meltbelow 290 (11 1 ;,Emample3..288 parts ofl-aminoldiphe. v nylsulphide-4= -oxamic acid :are. dissolved in hotwater withthe aid of a slight excess of ammonia; The excess of ammoniais 're-' movedby boiling, thexsolution cooled and after treating with 69parts of sodium nitrite,v V p of 36 percent hydrochloric acid. Thebright yellow suspension of the diaz'o compoundis poured on to amixtureof icev and 300 parts stirred for half an hour and is then added toa'solution of 337 parts of the sodium saltof. 2-phenylamino-5-naphthol7-sulphonic acid" containing 300 parts of sodium carbonate. The mixtureis stirred until coupling isgcomplete whenjit is; heated up and thedyestufi isolated by'the addition of common salt. It

Idyes viscose rayon in. bright bluish red shades; If in place'of'the2-p'he' 'iylamine-5 naphthol-7-sulphonic acid there is used a solutioncontaining 319 parts of: l-ainino-S A naphthol-2 4 -disul'phonicacidythe dyestufi 1 obtained dyes viscose rayon in 'violet shades.

Similarly the use of a solution of 315 parts of 2-henylamino-8-naphthol-6-sulphonic acid a ords a dyestufi giving browndyeings on wool fast to milling and stoving. This dyestuif as sodiumsalt is represented most probably by the constitution OH QOOaOQE-Os-O-Nm-KID- HG It yields on reduction-aminodiphenylsulhide-4-oxamic acid and, 2-phenylamino- :8 aminonaphthol6 sulphonic acid: It

dissolves in concentra ed sulphuric acid giving a grenish-blue solutionwhich changes to violet brown on gradual dilution with water ultimatelyyielding a brown precipitate.

Example .4.352 parts of l-aminodiphenyltrisulphide-tf-oXamic acid arediazotized with 69 parts. of sodium nitrite and 300 parts of 36 per centhydrochloric acid by the method described inEXample 3. The suspension isrun into a solution of 138 parts of salicylic acid and 600 parts ofsodium carbonate and stirred until coupling is complete.

1 The mixture is then heated up and the dyestufl' isolated by theaddition of common salt. It dyes cellulose acetate rayon in brightyellow shades, and wool a yellow shade fast to milling. If. in place ofthe salicylic acid there is used a solution of 239 parts of 2-amino-5-naphthoL7-sulphonic acid, the dyestuff obtained dyes viscoserayon in even yellowish red shades.

' Ewample -5.To the suspension of diazo compound obtained from 352 partsof 1- amino-diphenyltrisulphide-l-oXamic acid as described in Example 4there is added a neutral solution containing 254 parts of 1-4:Sl1l.-phophenyl-3-methyl-5-pyrazolone. The mixture is stirred until couplingis complete,

when it is made alkaline, heated up and thedyestuflf isolated by theaddition of common salt. It gives yellow dyeings on wool which are ofexcellent fastness to milling.

added a neutral'solution' containing 223 parts of'2-naphthylamine-6-sulphonic acid, the

dyestuif obtained dyes wool in orange-yellowv shades fast to milling andviscoserayon in very level orange yellow shades.

Having now particularly described and disclosed the nature of my saidinvention and in what manner the same is to be performed, I declare thatwhat I claim'is 1 1. In the process of 7 manufacturing new azo dyestuffsprobably represented in the form of the free acid by the formula ooonoongsnO-nflv-x I where nrepresents 1 or 3 and X represents the residue of acoupling component; the step which comprises combining a diazotized Ifin place of the pyrazolone solution there -isoxamic acid derivative of a4:4'-diaminodiphenylsulphide of the formula when n represents 1 or 3with an azo dyestufl component.

2. In the processof manufacturing new azo dyestuffs probably representedin the form of the free acid by the general formula where X representsthe residue of a coupling component; the step which comprises combininga diazotized oXamic acid derivative of the formula, Y

OOOH.CO.NOS NH1 l with an azo dyestuif component.

3. New azo dyestuffs which in theform of the free acid may berepresented by the probable general formula V p where n represents 1 or3 and X represents the residue of a coupling'component.

4. New azo dyestufis which in the form of the free acid may berepresented by the probable general formula (JOOROOJ W OSO-rhN-X H vwhere X represents the residue of a coupling component;

5. The new azo dyestuff which in the form of the free acid mayberepresented by the probable formula I on i H HOaS wherein n represents 1or 3, with one molecular proportion of oxalic acid, diazotizing theresulting oxamic acid derivative and coupling with an azo dyestuffcomponent.

7. The process of claim 6 wherein n represents'l.

8 The process of claim 6 wherein the diazotized oXamic acid derivativeis coupled with an amino naphthol sulphonic acid, the amino group ofwhich may be substituted.

9. The process of claim'6 wherein nrepresents 1 and the diazotizedoxamic acid derivative is coupled with an amino naphthol A v c H whereinn represents 1 or 3, 1' represents 1 or sulphonic acid, theamino groupof which may be substituted.

10. In the process of manufacturing new ,azo dyestufl's which in theform of the free acid may be represented by the probable formula rWhereinn represents 1 or 3, 1" represents 1 or 2 and R representshydrogen or an aryl group; the step which comprises. diazotizing anoxamic acid derivative of the probable formula and coupling theresulting diazo compound oooncoifO-srOrhn-x cooncogOsnOniN probableformula form of thefree acid maybe represented by the probable formula 2and R represents hydrogenor an aryl roup. 17 The new azo dyes of claim16 w crew 12 represents 1, 7" represents 1 andrR represents a phenylgroup.

18, The new azo dyestufi which in the form of the-free acid may berepresented by-the probable formula wherein X represents coupled2-phenylamiof the free acid may be represented bythe wherein Xrepresents coupled 1-amino-8-v naphthol-2 4-disulphonic acid.

In testimony whereof I aflixmy signature.

' RAINALD BRIGHTMAN.

wherein n represents 1 or 3 and X represents 7 the coupled residue of anaminonaphthol sulphonic acid, the amino group of which may besubstituted. I

13. The new azo dyestufl's ofclaim 12 V wherein 'n represents 1.

14. The new azo dyestuffs of claim 12 wherein the; coupled aminonaphtholsulphonic acid is selected from a group consisting of2-phenylamino-5-naphthol-7-sulphon-- ic acid,1-amino-8-naphthol-2:4-disulphonic acid,2-phenylamino-8-naphthol-6-sulphonic acid and2-amino-5-naphthol-7-sulphonicacid. 7 c a 15. The new dyestuffs of claim12 wherein V n represents 1 and the coupled aminonaphthol sulphonic acidis selected from a group consisting of 2-phenylamino-5-naphthol-7-sulphonic acid, 1-amino-8-naphthol-2:4=-disulphonic acid,25'phenylamino-8-naphthol-6-sul- I phonic acid and2-amino-5-naphtho1-7-sulphonic acid. a p r 16. The new azo dyestuffswhich in the Certificate of Correction Patent No. 1.805,?14. Granted May19,1931, to

RAINALI) BRIGHTMAN It is hereby certified that error appears in theprinted specification of the abovenumbered patent requiring correctionas follows: Page 1, strike out the formula between lines 15 to 17, andinsert mula between lines 14: ancl 17, and insert OH 121. between lines69 and 71, and insert d with these corrections therein that PatentOflice.

Page 3, claim 10, strike out the for Same page, claim 16, strike out theformu t the said Letters Patent should be rea form to the record of thecase in the is 7th day of July A. D. 1931.

and tha the same may con Signed and sealed th [SEAL] 4 M. J. MOORE,

A cting Co rwmissione'r 0 f Patents.

